US6365705B1 - Spiro-ammonium ionomer carboxylates - Google Patents
Spiro-ammonium ionomer carboxylates Download PDFInfo
- Publication number
- US6365705B1 US6365705B1 US09/699,710 US69971000A US6365705B1 US 6365705 B1 US6365705 B1 US 6365705B1 US 69971000 A US69971000 A US 69971000A US 6365705 B1 US6365705 B1 US 6365705B1
- Authority
- US
- United States
- Prior art keywords
- ionomer
- recurring units
- carboxylate
- nitrogen
- ammonium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920000554 ionomer Polymers 0.000 title claims abstract description 15
- 150000007942 carboxylates Chemical class 0.000 title claims abstract description 13
- 229920000642 polymer Polymers 0.000 claims abstract description 61
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 3
- -1 quaternary ammonium carboxylate Chemical class 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 13
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 12
- 125000004122 cyclic group Chemical group 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 150000003926 acrylamides Chemical class 0.000 claims description 5
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- 125000002947 alkylene group Chemical group 0.000 claims description 4
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- 125000001627 3 membered heterocyclic group Chemical group 0.000 claims 1
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- 239000000126 substance Substances 0.000 description 5
- 0 C.C.C.C.C.C.C.C.C1CC1.CB*(C)CC(=O)O.CB*(C)CC(=O)O.[Y].[Y] Chemical compound C.C.C.C.C.C.C.C.C1CC1.CB*(C)CC(=O)O.CB*(C)CC(=O)O.[Y].[Y] 0.000 description 4
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- 238000003786 synthesis reaction Methods 0.000 description 4
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
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- RCXFJYVHZBXWRS-UHFFFAOYSA-N 8-pyrimidin-2-yl-8-aza-5-azoniaspiro[4.5]decane Chemical compound C1CCC[N+]21CCN(C=1N=CC=CN=1)CC2 RCXFJYVHZBXWRS-UHFFFAOYSA-N 0.000 description 2
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- 229920001184 polypeptide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000001931 thermography Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
- C08K5/3417—Five-membered rings condensed with carbocyclic rings
Definitions
- This invention relates to novel polymers that have net negatively charged backbones and spiro-ammonium cations. These polymers are particularly useful in heat-sensitive printing plate formulations.
- thermally-sensitive polymers that are water-soluble or water-dispersible are of particular value.
- the ability of a polymer to undergo such thermally driven changes by means of a reaction in which small molecule byproducts are not emitted is also desirable for many chemical and coating processes in many industries.
- Low molecular weight (monomeric) spiro-ammonium salts (1-azoniaspiro salts) are known in the field of organic chemistry.
- Cationic polymers containing spiro-ammonium ions covalently bound within the main chain are also known in the art, having found uses as mordants. See, for example, Muellen et al, Polym. Bull. (Berlin), 1990, 24, 263, De Vynck et al, Macromol. Rapid. Commun, 1997, 18, 149, and U.S. Pat. No. 3,741,768 (Van Paesschen et al).
- ammonium cations described in the prior art are immobilized within the polymer backbone. This would affect their solubility and usefulness in thermally-sensitive systems. Moreover, it is highly unpredictable as to what interactions or compatibility they might have with other common ingredients in industrial and coating formulations (such as surfactants, colorants, and thickeners). From the perspective of synthetic feasibility, it is typically more difficult to incorporate specific units (in this case, a spiro-quaternary ammonium ring system) into the main chain of a polymer than it is to introduce a desired counterion.
- specific units in this case, a spiro-quaternary ammonium ring system
- This invention provides an ionomer having carboxylate recurring units in its backbone and an ammonium counterion for the carboxylate recurring units wherein one or more positively charged nitrogen atoms of the counterion are positioned at tetrahedral vertices of one or more spiro bicyclic ring systems.
- the polymers (ionomers) of this invention are specifically designed to undergo thermally driven nucleophilic substitution reactions in which the carboxylate moieties ionically bound to the polymer backbone attack the carbon atoms in the ⁇ -position in relation to the quaternary ammonium centers of spiro-ammonium counterions. This results in the cleavage of carbon-nitrogen bonds, the formation of ester bonds, and the dequaternization of the ammonium ions. This reaction will result in changes in solubility and surface energy of the polymer.
- Reactive Scheme 2 shows a similar reaction in which a dicationic counterion is used in the polymer. In that situation, the resulting polymer is crosslinked and no volatile compounds are emitted.
- the polymers of this invention may find utility in water-based thermally hardenable coating formulations. This class of novel materials is particularly useful for markets and applications having stringent environmental requirements. These polymers are also useful in thermal imaging applications, such as thermally-sensitive printing plates, as described in copending U.S. Ser. No. 09/454,151, filed Dec. 3, 1999 by Leon and Fleming.
- polymers of this invention can be derived from such common and inexpensive ethylenically unsaturated polymerizable monomers as acrylic acid and methacrylic acid, and hence can be easily copolymerized with other common monomers using known techniques and reliable methods.
- the polymers of this invention comprise random recurring units at least some of which comprise carboxylic acids groups and the particular spiro-ammonium cations described herein.
- the polymers generally have a molecular weight of at least 2000 Daltons and preferably of at least 5000 Daltons.
- the carboxylate-containing polymers can be chosen or derived from a variety of polymers and copolymer classes including but not limited to polyamic acids, polyesters, polyamides, polyurethanes, silicones, proteins (such as modified gelatins), polypeptides, and polymers and copolymers based on ethylenically unsaturated polymerizable monomers such as acrylates, methacrylates, acrylamides, methacrylamides, vinyl ethers, vinyl esters, maleic acid/anhydride, itaconic acid/anhydride, styrenics, acrylonitrile, and olefins such as butadiene, isoprene, propylene, and ethylene.
- the starting polymers can contain more than one type of carboxylic acid-containing monomer. Certain monomers, such as maleic acid/anhydride and itaconic acid/anhydride may contain more than one carboxylic acid unit.
- the polymers are represented by the following Structure I or II:
- This spacer unit can be any divalent aliphatic, alicyclic or aromatic group that does not adversely affect the polymer's heat-sensitivity.
- W can be a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms (such as methylene, ethylene, isopropylene, n-propylene and n-butylene), a substituted or unsubstituted arylene group having 6 to 10 carbon atoms in the arylene ring (such as m- or p-phenylene and naphthylenes), substituted or unsubstituted combinations of alkylene and arylene groups (such arylenealkylene, arylenealkylenearylene and alkylenearylenealkylene groups), and substituted or unsubstituted N-containing heterocyclic groups.
- alkylene group having 1 to 16 carbon atoms such as methylene, ethylene, isopropylene, n-propylene and n-butylene
- arylene group having 6 to 10 carbon atoms in the arylene ring such as m- or p-phenylene and naphthylenes
- any of these defined groups can be connected in a chain with one or more amino, carbonamido, oxy, thio, amido, oxycarbonyl, aminocarbonyl, alkoxycarbonyl, alkanoyloxy, alkanoylamino or alkaminocarbonyl groups.
- Particularly useful “W” spacers contains an ester or amide connected to an alkylene group or arylene group (as defined above), such as when the ester and amide groups are directed bonded to “A”.
- r can be 0 or 1 in Structure I, preferably r is 0.
- A represents recurring units derived from ethylenically unsaturated polymerizable acrylates, methacrylates, acrylamides, methacrylamides, maleic acid or anhydride, or itaconic acid or anhydride.
- Additional monomers that provide the recurring units represented by “B” in Structure I above include any useful hydrophilic or oleophilic ethylenically unsaturated polymerizable comonomers that may provide desired physical or chemical properties or which provide crosslinkable functionalities.
- One or more “B” monomers may be used to provide these recurring units, including but not limited to, acrylates, methacrylates, styrene and its derivatives, acrylamides, methacrylamides, olefins, vinyl halides, vinyl ethers, and any monomers (or precursor monomers) that contain carboxy groups (that do not have spiro-quaternary ammonium counterions).
- the quaternary ammonium counterions in the polymers can include any compounds that comprise a tetracoordinate nitrogen positioned at the vertex of two intersecting ring systems.
- these ring systems are represented by X, Y, and Y′ in Structures I and II taken with the illustrated nitrogen atoms.
- Y and Y′ independently comprise any combination of carbon, nitrogen, oxygen, sulfur, phosphorous or selenium atoms sufficient to complete one or more heterocyclic ring systems with the illustrated nitrogen atom, each ring system independently having at least three atoms.
- Y and Y′ independently complete ring systems with the illustrated nitrogen atom that can have from 3 to 9 atoms (carbon and heteroatoms).
- Such ring systems include, but are not limited to aziridine, azetidine, morpholine, piperidine, oxapyrrolidine, pyrrolidine, carbazole, indoline, and isoindoline rings. Additionally, the ring systems can contain one or more double bonds or may themselves be units in a more complex fused or compound ring system.
- X represents at least two additional carbon, nitrogen, oxygen or sulfur atoms that together with the two illustrated nitrogen atoms, complete at least a 4-membered heterocyclic ring system located between the ring systems defined by Y and Y′.
- the types of ring systems that define X can be similar to those defined by Y and Y′ except that they have at least four valencies available for bonding to the two illustrated nitrogen atoms.
- the individual atoms composing X, Y, and Y′ can contain substituents sufficient to fulfill the valency requirements.
- substituents include independently substituted or unsubstituted cyclic, branched, or linear alkyl groups having 1 to 20 carbon atoms [such as methyl, ethyl, n-propyl, isopropyl, t-butyl, hexyl, hydroxyethyl, 2-propanonyl, ethoxycarbonymethyl, benzyl, substituted benzyl (such as 4-methoxybenzyl, o-bromobenzyl, and p-trifluoromethylbenzyl), and cyanoalkyl], or substituted or unsubstituted aryl groups having 6 to 14 carbon atoms in the carbocyclic ring (such as phenyl, naphthyl, xylyl, p-methoxyphenyl, p-methylphenyl, m-me
- multi-cationic ionic species containing more than one quaternary ammonium unit covalently bonded together and having charges greater than +1 (for example +2 for diammonium ions, and +3 for triammonium ions) may be used in these novel polymers.
- n represents from about 1 to 100 mol % (preferably from about 50 to 100 mol %) and m represents 0 to about 99 mol % (preferably from 0 to about 50 mol %).
- Structure I could be interpreted to show polymers comprised of only two types of recurring units, it is intended to include terpolymers and other polymers derived from more than two ethylenically unsaturated polymerizable monomers.
- the spiro-ammonium ions of the present invention can be readily prepared using modifications of well known synthetic methods that are widely used for the synthesis of quaternary ammonium salts. These methods are described in many basic synthetic textbooks including March, Advanced Organic Chemistry, 3 rd Ed., John Wiley & Sons, New York, 1985. Such methods will be obvious to one skilled in organic synthesis.
- One particularly useful synthetic method involves the reaction of a cyclic, secondary amine with a compound containing two leaving groups (such as halide or sulfonate esters) that are positioned in such a way that makes ring closure a facile pathway. The reaction of ammonia with two equivalents of such a compound will yield a symmetric spiro-ammonium salt.
- the parent backbone polymers of this invention can be readily prepared using many methods that will be obvious to one skilled in the art. Many carboxylic acid or anhydride-containing polymers are commercially available. Others can be readily synthesized using preparative techniques that will be obvious to one skilled in the art.
- the carboxylic acid or anhydride-containing polymers can be converted to the desired quaternary ammonium carboxylate salt by a variety of methods including, but not necessarily limited to:
- All of the polymers were prepared by a general synthetic sequence consisting of: (1) the synthesis of a spiro-quaternary ammonium halide, (2) conversion of the halide to its hydroxide salt using silver (I) oxide, and (3) the neutralization of a carboxylic acid-containing polymer using the spiro-quaternary ammonium hydroxide to yield a solution of the desired polymer in methanol-water.
- the quaternary ammonium halide salts were characterized by 1 H NMR and electrospray mass spectrometry. For Polymers 1, 3, 4, and 5, the purity was additionally determined by reverse phase HPLC. In all cases, the halide salts were found to be at least 95% pure.
- the spiro-ammonium hydroxide salts were stored as solutions in water/methanol and were never isolated.
- the hydroxide concentrations of the solutions were determined by hydrochloric acid titration.
- the hydroxide salts were further characterized by electrospray mass spectrometry and the purity of the solutions that contained aromatic moieties (Polymers 1, 3, 4, and 5) were further checked by reverse phase HPLC. Due to their hygroscopic nature, the spiro-ammonium hydroxide salts and the spiro-ammonium carboxylate polymers were stored as solutions and were never isolated. The extent of neutralization was determined by monitoring the disappearance of the carboxylic acid IR band (1720 cm ⁇ 1 ) and the appearance of the corresponding carboxylate anion band (1550-1580 cm ⁇ 1 ).
- step B The product solution of step A was combined in a 500 ml round bottomed flask with 9:1 methanol:water (130 ml) and silver (I) oxide (16.59 g). The flask grew slightly warm and the undissolved solids turned from black to a dull gray. The reaction solution was allowed to stir for an hour at room temperature and the insoluble materials were filtered off. The filtrates were passed through a flash chromatography column packed with 300 cm 3 of DOWEX® 550A OH resin using a methanol eluent. The collected fractions were concentrated to a weight of 36 g by rotary evaporation. The concentration of hydroxide anion was determined to be 2.218 meq/g by HCl titration.
- Piperidine (Aldrich, 500 g) was slowly added to 500 g of 35-40% formaldehyde in an ice-water bath at such a rate as to maintain the temperature at 30-40° C. After the addition was finished, 500 ml of absolute ethanol was added in one portion and the solution was saturated with potassium carbonate. The upper layer was separated and extracted by rapid stirring with another 500 ml of ethanol. The combined ethanolic fractions were stirred over potassium carbonate, filtered, combined with 1 liter of benzene, and transferred to a distillation assembly. Heating was initiated and after ⁇ 1 liter of the benzene/ethanol/water azeotrope was collected, a second 1 liter of benzene was added and the distillation was continued.
- the product from the previous step (8 g) was combined in a 500 ml round bottomed flask with 80 g of 9:1 water:methanol and 10.4 g silver (I) oxide. The mixture was stirred at room temperature for one hour at which point the insoluble compounds had turned to a steel gray color. The silver salts were removed by vacuum filtration through a Teflon membrane filter and the filtrates were concentrated to 27.5 g using a rotary evaporator. The concentration of hydroxide anion was determined to be 1.14 meq/g by titration with hydrochloric acid.
- a 10% (w/w) solution of poly (methyl vinyl ether-co-maleic anhydride) was prepared by stirring 1.00 g of GANTREZ AN-139 polymer (ISP Technologies) in 9.0 g distilled water for an hour, at which point a homogeneous solution had formed. Methanol (2.34 g) was added with vigorous stirring followed by 3.84 g of the hydroxide solution from the previous step. Analysis by IR showed complete disappearance of the carboxylic acid band (1720 cm ⁇ 1 ) and the appearance of a carboxylate band (1572 cm ⁇ 1 ).
- the filtrates were concentrated to orange oil, dissolved in 200 ml methanol, adsorbed onto about 100 cm 3 silica gel, and loaded onto the top of a flash chromatography column packed with about 1000 cm 3 of silica gel.
- the column was first eluted with 1:1 ethyl acetate:hexane to remove an organic-soluble impurity, and then with methanol to elute the desired product.
- the collected methanolic solution was concentrated to yellowish oil on a rotary evaporator to provide 15.0 g of the purified spiro-indolinium bromide salt.
- Step B All of the purified product from Step A was dissolved in 150 ml of a 9:1 methanol:water mixture. It was then converted to the corresponding hydroxide salt with silver (I) oxide (27.34 g) in an analogous manner as described for Polymer 1 (Step B). A solution (41.9 g) of 1.300 meq/g of hydroxide anion was obtained.
- the crude product was purified by recrystallization from absolute ethanol and dried in a vacuum oven at 60° C. overnight to afford 6.60 g (67% yield) of fine white crystals.
- the product was characterized by 1 H NMR and electrospray mass spectrometry.
- step B The product from step A (7.39 g) was converted from the bromide to the hydroxide using 5.65 g silver (I) oxide and 70 ml of a 9:1 methanol:water mixture in an analogous manner as used for Polymer 1 (Step B). A solution (14.50 g) of 1.452 meq/g of hydroxide anion was obtained.
Abstract
Description
Claims (11)
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US09/699,710 US6365705B1 (en) | 2000-10-30 | 2000-10-30 | Spiro-ammonium ionomer carboxylates |
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6447978B1 (en) * | 1999-12-03 | 2002-09-10 | Kodak Polychrome Graphics Llc | Imaging member containing heat switchable polymer and method of use |
US6844140B1 (en) | 2003-12-29 | 2005-01-18 | Kodak Polychrome Graphics Llc | Method for reducing start up blinding in no-process lithographic printing plates |
US20100291203A1 (en) * | 1997-12-22 | 2010-11-18 | Purdue Pharma L.P. | Opioid Agonist/Antagonist Combinations |
CN108264513A (en) * | 2017-01-04 | 2018-07-10 | 三和涂料株式会社 | It is used to prepare the method for spiro quaternary ammonium salt |
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JP2021031459A (en) * | 2019-08-27 | 2021-03-01 | 東ソー株式会社 | Hexahydrobenzodipyrrole and production method thereof |
JP2021031348A (en) * | 2019-08-27 | 2021-03-01 | 東ソー株式会社 | Method for producing zeolite using hexahydro-benzo-dipyrrolium salt, and novel hexahydro-benzo-dipyrrolium salt |
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US10093677B2 (en) * | 2017-01-04 | 2018-10-09 | Samhwa Paints Industries Co., Ltd. | Method for preparing spiro quaternary ammonium salt |
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CN109762190B (en) * | 2018-12-28 | 2021-05-25 | 吉林大学 | Polyarylether anion exchange membrane material with side chain containing N-spiro quaternary ammonium salt group and preparation method thereof |
JP2021031459A (en) * | 2019-08-27 | 2021-03-01 | 東ソー株式会社 | Hexahydrobenzodipyrrole and production method thereof |
JP2021031348A (en) * | 2019-08-27 | 2021-03-01 | 東ソー株式会社 | Method for producing zeolite using hexahydro-benzo-dipyrrolium salt, and novel hexahydro-benzo-dipyrrolium salt |
JP2021031457A (en) * | 2019-08-27 | 2021-03-01 | 東ソー株式会社 | Hexahydro-benzo-dipyrrolium salt, and use thereof |
JP7249911B2 (en) | 2019-08-27 | 2023-03-31 | 東ソー株式会社 | Hexahydrobenzodipyrolium salt and use thereof |
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